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US20180354238A1 - Multilayer structure comprising a layer containing a fluoropolymer and acrylic copolymer - associated production method and tube - Google Patents

Multilayer structure comprising a layer containing a fluoropolymer and acrylic copolymer - associated production method and tube Download PDF

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Publication number
US20180354238A1
US20180354238A1 US15/781,204 US201615781204A US2018354238A1 US 20180354238 A1 US20180354238 A1 US 20180354238A1 US 201615781204 A US201615781204 A US 201615781204A US 2018354238 A1 US2018354238 A1 US 2018354238A1
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US
United States
Prior art keywords
layer
multilayer structure
functional groups
tube
olefinic polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
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US15/781,204
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English (en)
Inventor
Florent ABRGALL
Samuel Devisme
Thomas LABOUR
Jérôme RONDIN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
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Arkema France SA
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Publication of US20180354238A1 publication Critical patent/US20180354238A1/en
Assigned to ARKEMA FRANCE reassignment ARKEMA FRANCE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LABOUR, Thomas, DEVISME, SAMUEL, RONDIN, JEROME, ABGRALL, Florent
Abandoned legal-status Critical Current

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00Layered products having a non-planar shape
    • B32B1/08Tubular products
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04Interconnection of layers
    • B32B7/10Interconnection of layers at least one layer having inter-reactive properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04Interconnection of layers
    • B32B7/12Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16LPIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00Hoses, i.e. flexible pipes
    • F16L11/04Hoses, i.e. flexible pipes made of rubber or flexible plastics
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00Layers arrangement
    • B32B2250/24All layers being polymeric
    • B32B2250/246All polymers belonging to those covered by groups B32B27/32 and B32B27/30
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00Resin or rubber layer containing a blend of at least two different polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2597/00Tubular articles, e.g. hoses, pipes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/13Hollow or container type article [e.g., tube, vase, etc.]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/13Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352Polymer or resin containing [i.e., natural or synthetic]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/13Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1379Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit

Definitions

  • the present invention relates to a multilayer structure capable of being used in particular in the transport of water.
  • Fluoropolymers in particular the polymers obtained from vinylidene fluoride, have a great chemical inertness, which makes them in particular suitable for transporting numerous chemicals.
  • Their resistance to chlorinated agents chlorine dioxide, chloramines, sodium hypochlorite, etc. makes them excellent candidates for applications in the transport of water, in particular hot water, especially in a hospital and sanitary environment, where aggressive treatments based on chlorinated agents are commonly used.
  • the drinking water conduits or lines must meet very strict criteria.
  • the line must not lose its mechanical properties owing to the treated water that it contains; it must in particular be resistant to aging, not be perforated or break and be flexible to facilitate the installation thereof. It must furthermore preserve the quality of the water transported: the structure of the line should only emit a small amount of given chemical compounds into the water transported and/or should prevent the accumulation of a biofilm on the inner surface of the line.
  • the line should also be easy to manufacture, for example by coextrusion.
  • Polyolefins and in particular polyethylenes have mechanical properties that make them suitable to be used in the form of a tube for a line. Nevertheless, the limited chemical resistance of these polymers makes them sensitive to the chlorinated agents used for treating the water, more particularly under high temperature conditions (above 70° C.).
  • An inner fluoropolymer layer combined with a polyolefin layer may thus protect the latter from the action of these aggressive chemicals contained in the water.
  • these polymers are incompatible; it is therefore difficult to make the fluoropolymers adhere to the polyolefins.
  • Document DE 202011103017 U1 describes lines for drinking water that comprise a tube made of PVDF (polyvinylidene fluoride).
  • This tube is covered with an aluminum foil and attached to the latter by means of a binder; the aluminum foil is itself covered with a layer of polyethylene.
  • the aluminum foil gives the line a low permeation to gases and limits the migration of the chemical constituents of the polyethylene toward the water.
  • the presence of the aluminum foil makes the line expensive and difficult to manufacture.
  • Document FR 2 892 171 describes a tube that can be used as a line for transporting water.
  • This tube comprises a multilayer structure that comprises a layer C2 containing a functionalized fluoropolymer bonded to a layer C3 or C4 containing a polyolefin. It turns out that this type of multilayer structure withstands aging poorly when it is in contact with hot water.
  • One problem that the invention intends to solve is to provide a multilayer structure that has a good adhesion between a layer comprising a fluoropolymer and a layer of polymer incompatible with said fluoropolymer.
  • Another objective of the present invention is to provide a multilayer structure having a satisfactory degree of adhesion, for example substantially greater than or equal to 30 N/cm between the layer comprising a fluoropolymer and the incompatible polymer layer, this adhesion being measured by longitudinal peeling, i.e. longitudinal cutting of a tube and measurement of the adhesion by the “imposed 90° peel” method at a temperature of 23° C. and a pull rate of 50 mm/min, the lever arm composed of the layer(s) containing the fluoropolymer having a total thickness of between 200 and 400 ⁇ m.
  • Another objective of the present invention is to provide a multilayer structure that can withstand aging (especially over at least 2000 hours) in water at a temperature equal to or above 80° C., in particular equal to 95° C., this water possibly containing chlorinated agents used for treating the water.
  • the present invention relates to a multilayer structure comprising, in order:
  • the various layers forming the structure may also comprise additives, especially rheological additives, impact modifiers, pigments, and also any other additives known to a person skilled in the art.
  • the multilayer structure according to the invention preferably comprises a layer A in direct contact with the drinking water.
  • the presence of this layer A ensures a better chemical resistance to the water treatment agents and a better resistance to the formation of biofilm at the surface of the material in direct contact with the drinking water.
  • the present invention also relates to a tube for transporting fluids, especially liquids such as water or liquids for food use, said tube being more particularly suitable for transporting drinking water, especially hot drinking water.
  • the present invention relates to a multilayer structure comprising, in order:
  • the monomers bearing functional groups Y are unsaturated epoxides or vinyl esters of saturated carboxylic acids.
  • the layer B comprises at least one fluoropolymer and one acrylic copolymer comprising monomers having a plurality of functional groups X.
  • the functional groups X are carboxyl groups.
  • the functional groups X are carboxylic acid anhydride groups.
  • the functional groups X are mixtures of carboxyl and carboxylic acid anhydride groups.
  • the acrylic copolymer is a copolymer of methyl methacrylate and glutaric anhydride or a copolymer of methyl methacrylate and methacrylic acid or a mixture of these two copolymers.
  • the acrylic copolymer of said layer B comprises, by weight, from 1% to 50%, preferentially between 1% and 25%, limits included, of monomers bearing a function X described above.
  • said layer B is free of alpha-olefinic polymer comprising at least one functional group chosen from carboxyl, acid anhydride, hydroxyl and epoxy groups.
  • the fluoropolymer of layer A and that of layer B are not limiting according to the invention. They may be identical or different in the two layers.
  • the layers may also comprise a mixture of at least two fluoropolymers, this mixture being identical or different in the layers A and B.
  • the fluoropolymer(s) of the layers A and B is/are chosen from homopolymers of vinylidene fluoride (PVDF) and copolymers of vinylidene fluoride and of at least one other comonomer.
  • PVDF vinylidene fluoride
  • the comonomer of the VDF is chosen from vinyl fluoride, trifluoroethylene (VF3), chlorotrifluoroethylene (CTFE), 1,2-difluoroethylene, tetrafluoroethylene (TFE), hexafluoropropylene (HFP), perfluoro(alkyl vinyl ethers) such as perfluoro(methyl vinyl ether) (PMVE), perfluoro(ethyl vinyl ether) (PEVE), perfluoro(propyl vinyl ether) (PPVE), perfluoro(1,3-dioxozole); perfluoro(2,2-dimethyl-1,3-dioxole) (PDD), the product of formula CF 2 ⁇ CFOCF 2 CF(CF 3 )OCF 2 CF 2 X in which X is SO 2 F, CO 2 H, CH 2 OH; CH 2 OCN or CH 2 OPO 3 H, the product of formula CF 2 ⁇ CFOCF 2 CF 2 SO
  • the comonomer is hexafluoropropylene (HFP).
  • the fluoropolymer of the layer A is a vinylidene fluoride homopolymer
  • the fluoropolymer of the layer B is also a vinylidene fluoride homopolymer but different from that of the layer A.
  • the layer C comprises, and preferably consists of, at least one first olefinic polymer comprising monomers having functional groups Y capable of interacting with the functional groups X.
  • the monomers bearing functional groups Y are chosen from:
  • the first olefinic polymer is a copolymer of ethylene and of at least one unsaturated polar monomer bearing functions Y from the preceding list which contains, by weight, at least 50%, advantageously more than 60% and preferably at least 65% of ethylene.
  • the first olefinic polymer is a terpolymer of ethylene, of at least one unsaturated polar monomer bearing functions Y from the preceding list and of C 1 -C 8 alkyl (meth)acrylates, in particular methyl, propyl, butyl, 2-ethylhexyl, isobutyl or cyclohexyl (meth)acrylate.
  • This terpolymer contains, by weight, at least 50%, advantageously more than 60% and preferably at least 65% of ethylene.
  • This first olefinic polymer may comprise, by weight, from 50% to 99.9% of ethylene, preferably from 60% to 99.9%, more preferentially still from 65% to 99.9% and from 0.1% to 50%, preferably from 0.1% to 40%, more preferentially still from 0.1% to 35% of at least one unsaturated polar monomer bearing functions Y from the preceding list.
  • the limits of the aforementioned intervals correspond to values by weight that the olefinic polymer of the invention may contain.
  • the structure according to the invention comprises an intermediate layer D.
  • the intermediate layer D comprises at least one second olefinic polymer comprising monomers having functional groups Z capable of interacting with said functional groups Y, said second olefinic polymer being different from that/those included in said layer C.
  • the functional groups Z are chosen from unsaturated carboxylic acids, unsaturated dicarboxylic acids having 4 to 10 carbon atoms and anhydride derivatives thereof
  • Said second olefinic polymer is chosen from the polymers obtained by grafting at least one unsaturated polar monomer having a functional group Z to at least one propylene homopolymer or one copolymer of propylene and of an unsaturated polar monomer chosen from C 1 -C 8 alkyl esters or glycidyl esters of unsaturated carboxylic acids, or salts of unsaturated carboxylic acids or a mixture thereof.
  • the polymer comprises, by weight, an amount of said grafting monomer equal to or less than 5%.
  • the second olefinic polymer is preferably, independently of the other constituents of the other layers, a maleic anhydride-grafted polypropylene.
  • said multilayer structure optionally comprises the layer A, the layers B and C and a layer E.
  • the layer E comprises at least one polymer, and in particular a third olefinic polymer incompatible with said fluoropolymer of said layer A and/or of said layer B.
  • said polymer incompatible with the layer E is chosen from ethylene homopolymers, copolymers of ethylene and of at least one other monomer chosen from alpha-olefins, alkyl acrylates, vinyl acetates and the mixtures of these polymers.
  • the incompatible polymer contained in the layer E denotes a polymer predominantly comprising ethylene and/or propylene monomers. It may be a polyethylene, homopolymer or copolymer, the comonomer being chosen from alpha-olefins (especially propylene, butene, hexene, octene), alkyl acrylates and vinyl acetates. It may also be a propylene, homopolymer or copolymer, the comonomer being chosen from alpha-olefins (especially ethylene, butene, hexene, octene). The incompatible polymer may also be a mixture of these various polymers.
  • the polyethylene may especially be high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), very low-density polyethylene (VLDPE).
  • the polyethylene may be obtained using a Ziegler-Natta, Phillips or metallocene-type catalyst or else using the high-pressure process. It may also be a crosslinked polyethylene (PEX).
  • the PEX has, compared to a non-crosslinked PE, better mechanical properties (especially as regards the crack resistance) and a better chemical resistance.
  • the polyethylene may be crosslinked using a radical initiator of peroxide type (PEX-a).
  • the crosslinked polyethylene may also be, for example, a polyethylene comprising hydrolyzable silane groups (PEX-b) enabling the formation of Si—O—Si bonds that link the polyethylene chains together.
  • the polyethylene may also be crosslinked using radiation, for example gamma radiation (PEX-c).
  • said polymer of said layer E is preferably chosen from propylene homopolymers, copolymers of propylene and of an alpha-olefin and the mixtures of these polymers.
  • the polypropylene is preferably an isotactic or syndiotactic polypropylene.
  • the process for manufacturing the multilayer structure according to the invention is not limiting. It may be obtained, for example, by coextrusion.
  • the multilayer structure according to the invention may make it possible to form tubes, that can be used as a line for transporting fluids, especially liquids, in particular for transporting water, advantageously drinking water and hot drinking water in particular.
  • the thickness of the multilayer structure according to the invention varies from 0.5 to 10 mm, preferably from 0.8 to 5 mm and more preferably still from 1 to 3 mm, limits included.
  • said layer E is the outer layer of said tube. It provides the mechanical strength of the tube.
  • the tube may comprise an inner layer A which prevents the formation of biofilm on the inner surface of the tube.
  • the combination of the layers B and C makes it possible to ensure a high adhesion between the various layers of the structure, even in the case of hot water circulation.
  • the tube may comprise the layers B, C and E or the layers A, B, C and E or the layers B, C, D and E or the layers A, B, C, D and E.
  • it comprises the layers A, B, C and E.
  • the layer D is located between the layer C and the layer E.
  • the present invention also relates to the use of a tube comprising the layers B, C and E for transporting fluids, especially liquids, in particular for transporting water, for example drinking water and domestic supply water, and especially hot water.
  • the present invention also relates to the use of a tube comprising the aforementioned layers B, C, D and E for transporting drinking water.
  • the present invention also relates to the use of a tube comprising the aforementioned layers B, C, D and E for transporting drinking water and especially hot drinking water.
  • the present invention also relates to the use of a tube comprising the aforementioned layers A, B, C, D and E for transporting drinking water and especially hot drinking water.
  • the layers A and B may contain one or more identical fluoropolymers or different fluoropolymers.
  • interact with reference to the functional groups X, Y and Z encompasses any type of interaction capable of giving rise to the bonding of the layers; it may be a chemical reaction between the functional groups of the layers in contact, diffusion of chains at the interface, the macromolecules of one layer being embedded in those of the adjacent layer, intermolecular bonds of van der Waals type or hydrogen bonds, or a mixture of these interactions.
  • acrylic copolymer comprising monomers having a plurality of functional groups X contained in the layer B, denotes a copolymer comprising:
  • R 1 and R 2 represent a hydrogen atom or a linear or branched alkyl having from 1 to 20 carbon atoms; it being possible for R 1 and R 2 to be identical or different;
  • R 3 is a hydrogen atom or a linear or branched alkyl containing one to twenty carbon atoms.
  • the latter unit may be in its acid form, but also in its anhydride derivatives or a mixture of these. When it is in anhydride form, this unit may be represented by the formula:
  • the acrylic copolymer comprises up to 50% by weight of the unit in acid form or its anhydride derivative or a mixture of the two.
  • the acrylic copolymer comprises up to 25% by weight of the unit in acid form or its anhydride derivative or a mixture of these.
  • R 1 and R 2 represent the methyl radical.
  • the binder is based on PMMA.
  • R 3 represents the hydrogen or methyl radical in the case where the unit that bears it is in acid form
  • R 4 and R 5 represent the hydrogen or methyl radical in the case where the unit is in anhydride form.
  • drinking water denotes water that has undergone a potabilization treatment and that therefore contains water treatment chemicals such as those mentioned with reference to the prior art.
  • suitable for transporting drinking water means that the polymer in question contains components that all appear on a list of components considered to be suitable for transporting drinking water chosen from the following documents: “WRAS certificate according to Standard B S6920” for the United Kingdom, “KTW certificate to Regulations KTW 1.3.13” for Germany, “KIWA certificate according to Regulations BRL 2013” for the Netherlands, the ACS certificate according to the circular published by the French Department of Health: DSG/VS4 no. 2000/232 dated 27 Apr. 2000 and the Italian decree D.M. no. 174 (ministerial decree No. 174 dated Jun. 4, 2007).
  • the multilayer tube S1 is formed of four successive layers (from the inside to the outside):
  • Layer B PVDF-2+acrylic copolymer chosen from CA-1, CA-2, CA-3 or PVDF-3 (comparative example)
  • the multilayer tube S2 is formed of five successive layers (from the inside to the outside):
  • Layer B PVDF-2+acrylic copolymer chosen from CA-1, CA-2, CA-3 or PVDF-3 (comparative example)
  • the multilayer tube S3 is formed of three successive layers (from the inside to the outside):
  • Layer B PVDF-2+acrylic copolymer chosen from CA-1, CA-2, CA-3 or PVDF-3 (comparative example)
  • the mixtures of PVDF-2 and of acrylic copolymer used in the layer B of these structures S1, S2 and S3 are prepared beforehand in a co-rotating twin-screw extruder under conditions that comply with the rules of the art, at a setpoint temperature of 220° C.
  • the inter-layer adhesion is measured by a peel test according to the “imposed 90° peel” method at a temperature of 23° C. and a pull rate of 50 mm/min.
  • the lever arm is composed of the layers A and B and has a total thickness of between 200 and 400 ⁇ m. The interface under strain is thus the one between the layers B and C.
  • a multilayer tube of structure S1 is produced by coextrusion using a device manufactured by the company McNeil Akron Repiquet. The coextrusion of these products is carried out at a temperature of 245° C.
  • the tube has an external diameter of 20 mm and a total thickness of 2 mm.
  • the thickness distribution within the structure is the following:
  • the nature and the concentration of the acrylic copolymer within the layer B is variable.
  • the polymer PVDF-3 is used for the layer B.
  • Table I below presents the various mixtures used in the layer B and the results of the adhesion tests.
  • the number indicated in the bottom of each box corresponds to the standard deviation of the adhesion value indicated above.
  • N.P. indicated in Table II indicate that the initiation cannot be propagated which means that the adhesion between the layers B and C is so high that, by exerting a force on the lever arm, its rupture stress is exceeded and the sample breaks without being able to separate the aforementioned two layers.
  • adhesions of greater than 40 N/cm are achieved with each of the 3 acrylic copolymers tested and are maintained after aging.
  • the use of a binder according to the invention comprising an acrylic copolymer bearing a functional group X therefore makes it possible to obtain an improved adhesion relative to the functionalized PVDF, PVDF-3.
  • the use of the latter clearly induces a gradual loss of adhesion at the interface between the layers B and C during exposure to water at 95° C., followed by cohesive failure at the interface between the layers.
  • the multilayer tube according to the invention thus has a better resistance to aging, especially in hot water.
  • the adhesion in hot water after 1000 h is substantially the same as that obtained after 2000 h and remains above the threshold of 30 N/cm.
  • a multilayer tube of structure S1 is produced by coextrusion using a device manufactured by the company McNeil Akron Repiquet. The coextrusion of these products is carried out at a temperature of 245° C.
  • the tube has an external diameter of 20 mm and a total thickness of 2 mm.
  • the thickness of the layer B is variable within the structure, which leads to the following thickness distribution:
  • the nature and the concentration of the acrylic copolymer within the layer B is variable.
  • the polymer PVDF-3 is used in the layer B.
  • the adhesion measurements at the interface between the layers B and C are presented in Table II.
  • the presence of anhydride groups therefore enables a better maintenance of the adhesion in this structure.
  • a multilayer tube of structure S2 is produced by coextrusion using a device manufactured by the company McNeil Akron Repiquet. The coextrusion of these products is carried out at a temperature of 245° C.
  • the tube has an external diameter of 32 mm and a total thickness of 3 mm.
  • the thickness distribution within the structure is the following:
  • the nature and the concentration of the acrylic copolymer within the layer B is variable.
  • the polymer PVDF-3 is used in the layer B.
  • Table III below presents the various mixtures used in the layer B and the adhesions generated at the interface between the layers B and C.
  • Adhesions of greater than 40 N/cm are achieved with each of the 3 acrylic copolymers tested and are maintained after aging. This is not the case when a functionalized PVDF, PVDF-3, is used as binder, with which a significant loss of adhesion is observed after 1000 h of aging in water at 95° C.
  • Multilayer tubes of structure S1 and S3 are produced by coextrusion using a device manufactured by the company McNeil Akron Repiquet. The coextrusion of these products is carried out at a temperature of 245° C.
  • the tube has an external diameter of 20 mm and a total thickness of 2 mm.
  • the thickness distribution within the structures is the following:
  • the total thickness of the layers A and B containing fluoropolymers remains identical in the tubes of the 2 structures.
  • the nature and the concentration of the acrylic copolymer within the layer B is variable.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Laminated Bodies (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)
US15/781,204 2015-12-08 2016-12-06 Multilayer structure comprising a layer containing a fluoropolymer and acrylic copolymer - associated production method and tube Abandoned US20180354238A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR1561980 2015-12-08
FR1561980A FR3044585B1 (fr) 2015-12-08 2015-12-08 Structure multicouche comprenant une couche contenant un polymere fluore et copolymere acrylique - procede de fabrication et tube associes
PCT/FR2016/053232 WO2017098139A1 (fr) 2015-12-08 2016-12-06 Structure multicouche comprenant une couche contenant un polymère fluore et copolymère acrylique - procédé de fabrication et tube associés

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US15/781,204 Abandoned US20180354238A1 (en) 2015-12-08 2016-12-06 Multilayer structure comprising a layer containing a fluoropolymer and acrylic copolymer - associated production method and tube

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EP (1) EP3386744B1 (ru)
JP (1) JP6869984B2 (ru)
KR (1) KR20180089504A (ru)
CN (1) CN108472924B (ru)
CA (1) CA3006907A1 (ru)
ES (1) ES2789755T3 (ru)
FR (1) FR3044585B1 (ru)
PL (1) PL3386744T3 (ru)
RU (1) RU2725379C2 (ru)
WO (1) WO2017098139A1 (ru)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI757055B (zh) * 2020-01-16 2022-03-01 日商旭化成建材股份有限公司 酚樹脂發泡體積層板及複合板

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0313670Y2 (ru) * 1986-12-25 1991-03-28
FR2659085B1 (fr) * 1990-03-02 1992-05-15 Atochem Composition coextrudable avec le polyfluorure de vinylidene permettant l'adhesion de ce dernier avec une resine polymerique non compatible - composite obtenu avec cette composition.
FR2757444B1 (fr) * 1996-12-20 1999-02-05 Nyltech Italia Structure multicouche a base de plastique et tube a structure multicouche
BE1012088A3 (fr) * 1998-07-27 2000-04-04 Solvay Adhesif polymerique et structures a couches polymeriques multiples, leur procede de preparation et leur utilisation.
FR2804064B1 (fr) * 2000-01-26 2002-03-29 Atofina Film multicouche thermoformable pour la protection de substrats et objets obtenus
AU2002241008A1 (en) * 2001-02-06 2002-08-19 Atofina Multilayer structure having a fluorinated polymer layer
US20050069710A1 (en) * 2001-11-29 2005-03-31 Anthony Bonnet Thermoformable multilayer film based on acrylic polymer for protecting substrates and resulting objects
EP1405872A1 (fr) * 2002-10-03 2004-04-07 Atofina Utilisation d'un film à base de PVDF, de PMMA ou leur mélange pour recouvrir des objets en matériau thermodur
TWI273087B (en) * 2003-12-01 2007-02-11 Arkema Use of a hose based on an irradiation-grafted fluoropolymer for transporting petrol in service station
DE102004048776A1 (de) * 2004-10-07 2006-04-13 Degussa Ag Mehrschichtverbund mit EVOH-Schicht und Schutzschicht
DE102004048777A1 (de) * 2004-10-07 2006-04-13 Degussa Ag Mehrschichtverbund mit Polyesterschicht und Schutzschicht
FR2886707B1 (fr) * 2005-06-02 2007-08-17 Arkema Sa Utilisation d'un tube a base de polymere fluore greffe par irradiation pour le transport de fluides sous pression
FR2892171B1 (fr) * 2005-10-13 2008-04-18 Arkema Sa Tube multicouche a base de polymere fluore modifie
FR2904867B1 (fr) * 2006-08-08 2008-09-19 Arkema France Tube multicouche pour le transport d'eau ou de gaz

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI757055B (zh) * 2020-01-16 2022-03-01 日商旭化成建材股份有限公司 酚樹脂發泡體積層板及複合板
US12269249B2 (en) 2020-01-16 2025-04-08 Asahi Kasei Construction Materials Corporation Phenolic resin foam laminate board and composite board

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CA3006907A1 (fr) 2017-06-15
JP6869984B2 (ja) 2021-05-12
JP2019505408A (ja) 2019-02-28
EP3386744A1 (fr) 2018-10-17
WO2017098139A1 (fr) 2017-06-15
RU2018124810A3 (ru) 2020-04-09
FR3044585B1 (fr) 2020-01-31
CN108472924A (zh) 2018-08-31
PL3386744T3 (pl) 2020-07-27
FR3044585A1 (fr) 2017-06-09
EP3386744B1 (fr) 2020-04-08
ES2789755T3 (es) 2020-10-26
KR20180089504A (ko) 2018-08-08
RU2018124810A (ru) 2020-01-10
RU2725379C2 (ru) 2020-07-02
CN108472924B (zh) 2020-12-01

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